Cleaning compositions



United States Patent Unite 3,095,5'8l Patented June 25, 1953 This invention relates to new compositions possessing improved surface active properties and to new detergent or cleaning compositions containing an alkyl substituted tertiary acetylenic hexynol, more particularly 3,5-dimethyl- 1-hexyn-3-ol.

A great many different cleaning formulations have been used in the past for cleaning surfaces such as glass, painted walls, woodwork, and so forth. Generally these cleaning compositions contain a detergent and when applied to a surface such as glass leave a film after their cleaning function has been performed. This residual film acts as a trap and collects dirt. The surface thus again becomes dirty even more rapidly than the same surface would become dirty in the absence of the residual Many attempts have been made to produce a so-called volatile cleaning or detergent composition. Theoretically, such a volatile composition when applied to a surface would perform its cleaning function and then completely evaporate, leaving the clean surface free of any residual film which would enhance the subsequent collection of dirt or soil. Volatile compositions have been prepared in the past which will completely evaporate after use leaving the surface devoid of any residual film, but such cleaning compositions will not adequately or sufficiently clean the surface desired.

Another type of cleaning or detergent composition commonly used, especially for glass, is generally composed of water, an alcohol such as isopropanol, and a small amount of a nonvolatile detergent such as fairly high molecular weight polyoxypropylene glycol-ethylene oxide addition products. The nonvolatile detergent is generally present in an amount of about 1 percent by volume. Since the detergent used in such formulations is nonvolatile, a soil collecting residual film is left on the surface on which it was used after it had performed its cleaning function.

These cleaning formulations generally contain an appreciable amount of water to render them as inexpensive as possible. The purpose of the addition of the alcohol is to make the formulation more volatile. Other materials as well as other alcohols in place of isopropanol can be used for this purpose as will be understood by those skilled in the art.

The object of this invention is to produce a cleaning or detergent composition having an increased cleaning ability and one which will also reduce and leave a minimal film deposit on the surface after the cleaning composition has performed its function.

A further object of this invention is to produce a cleaning composition which will completely evaporate after it has been used to perform its cleaning function and which will adequately and sufiiciently clean the surface desired with a minimum of rubbing.

This invention relates to the addition of a small amount of an alkyl substituted acetylenic tertiary alcohol, namely 3,5-dimethyl-l-hexyn-3-ol, to a cleaning composition containing a small amount of a nonvolatile detergent and advantageously in conjunction with a volatile alcohol such as isopropanol and water.

3,5-dimethyll-hexyn-3-ol is completely volatile as an entity and does not decompose or leave behind any matter of decomposition which might be film forming.

The 3,5-dimethyl-l-hexyn-3-ol is advantageously employed in partial replacement of the nonvolatile detergent employed in the cleaning composition as Well as in partial replacement of the volatile alcohol.

The 3,5-dimethyl-1-hexyn-3-ol acts synergistically when used in combination with a nonvolatile detergent and actually increases the cleaning power of the composition. This synergistic action permits the use of less nonvolatile detergents in the compositions while still retaining an equivalent or even greater cleaning power and at the same time materially reduces the formation of any residual film caused by the nonvolatile detergent due to its decreased concentration. The addition of the hexynol to these compositions thus results in a cleaning composition having greater cleaning power or the equivalent cleaning power and one which will also leave a minimal residual film deposit and thus prevent the rapid collection of soil due to the presence of larger amounts of residual films.

Other groups can be substituted on the carbon chain of the 3,5-dimethyl-1-hexyn-3ol in place of the two methyl groups present in the above compound so long as the molecular weight is not significantly increased or decreased so as not to upset the unique balance of volatility and surface action properties possessed by this compound as will be understood by those skilled in the art.

The dimethyl hexynol can be used in conjunction with various nonvolatile detergents or surface active agents. Nonvolatile detergents or surface active agents which can be used according to this invention in conjunction with the dimethyl hexynol include anionic agents such as sulfated or sulfonated oils such as castor oil, alkyl aryl sulfonates such as sodium dodecyl benzene sulfonates, sulfated and sulfonated amides and amines such as Igepon T, sulfated and sulfonated esters and ethers such as sodium salt of dioctyl sulfosuccinate and the sulfated or sulfonated alkyl aryl polyglycol ethers, alkyl sulfates such as sodium lauryl sulfate, and alkyl sulfonates; nonionic agents such as polyhydric alcohol fatty acid esters such as diglycol laurate and sorbitan monolaurate, polyoxypropylene glycol-ethylene oxide polymers, polyalkylene glycol esters, oxyethylated fatty acid partial esters of polyhydric alcohols, ethylene oxide-fatty alcohol condensates, alkyl aryl polyglycol others such as nonyl phenol-ethylene oxide condensate, polyglycol thioethers, and ethoxylated acid amides; and cationic agents such as salts of primary and tertiary amines such as hexadecyl amine hydroacetate, quaternary ammonium salts such as hexadecyl dimethyl benzyl ammonium chloride, salts of amino amides such as monostearoyl diethylene triamine dihydroacetate, quaternary ammonium salts of amino amides, quaternary derivatives of irnidazolines, and quaternary salts of amino esters. In addition to synergistically improving the wetting action of these other surface active agents, the acetylenic alcohol will in many cases suppress foam formation.

The use of the dimethyl hexynol together with polyoxypropylene glycol-ethylene oxide polymers or addition products has been found to be particularly advantageous.

The dimethyl hexynol can be employed in the cleaning or detergent compositions in conjunction with a nonvolatile detergent or surface active agent advantageously in proportions from 0.1 to 2 percent by volume.

The Draves test is an empirical wetting test that very nearly simulates practical wetting. The Draves test was thus used to evaluate the compositions of this invention.

The Draves test for determining wetting action is described in the American Association of Textile Chemists and Colorists Yearbook, 17, 216-222 (1940), and briefly is performed as follows:

A standard skein of Kier-boiled cotton thread weighing 5.00 g. (+.10 g.) is formed into a double loop. The length of the loop is about seven inches. A copper-S- hook weighing 3.00 g. is hooked through the bottom.

A piece of linen thread is tied to the other loop of the Shock and at a distance of three inches along the thread from the hook it is tied to a 40.00 g. weight.

The liquid to be tested is placed in a cylinder two inches in diameter and twelve inches deep. About 750 ml. are required.

The skein is held in the hand and the weight is lowered gently into the liquid. The skein is released just as the S-hook reaches the surface of the liquid.

A stop watch is used to measure the time interval from the moment the bottom of the skein breaks the surface of the liquid'until the S-hook sinks to the bottom (carrying the skein with it). The elapsed time is a measure of the wetting power, a shorter time indicating greater wetting power. I

All tests were made at 25 C. unless indicated otherwise. All solutions are in distilled water and are made upv to the concentration shown in the data table.

Examples Draves Sinking Time (seconds) at 25 0.

.0.5 3,5-dlmethyl-l-hexyn-3-0l .0.5 100% nonyl phenoxy pol hylene ethane (Igcpal -880) 0.48 3,5-dimethyl-l-hcXyn-3-01 0.02 100% nonyl phenoxy polyoxyethylene ethanol .0.5 an alkyl phenyl ether'of polyethylene glycol (Tergitol NP-35) 0.48 3,5-dimethyl-l-hexyn-3-ol 0.02 an alkyl phenyl ether of polyethylene glycol 6. 0.1 a ditertiaryacetylenlc glycol (Surfivnol 104) instantaneous 7. 0.48 3,5-dirnethyl-l-hexyn-3-0l 0.02 a dltertiary acctylenic glycol 14 8. 0.5 ahighly concentrated alkyl aryl sodium sulfonate (Nacconol-NRSF) 3 9. 0.48 3,5-dimethyl-l-hexyn-3-ol 0.02 a highly concentrated alkyl aryl sodium sulfonate I 6 10. 0.5 a sodium salt of condensed aryl sulfonic acid 300 (Tarnol) 11. 0.48 3,5-din1ethyl-l-hexyn-3-ol 0.02 a sodium salt of condensed aryl sulfonlc acid.;

In the above examples, 7 and 9, the use of 3,5-dimethyl-lhexyn-3-ol in combination with the nonvolatile detergents actually resulted in a decrease of wetting power according to the Draves test. The decrease in the wetting power, however, is not considered to be significant, and the advantage of being able to produce a cleaning composition with a very small amount of a nonvolatile detergent which will leave a minimum film after use is still very important together with a small decrease in the wetting power of'the nonvolatile detergent.

The following are examples of typical glass cleaning formulations using the 3,5-dimethyl-1-hexyn-3-01 of this invention: 7

Parts by volume Isopropanol (99%) 35.00 Diethylene glycol monoethyl ether-.. 7.25 Alkyl phenyl ether of polyethylene glycol (Tergitol Anionic) Y 3,5-dimethyl-1-hexyn-3-ol 0.48 Water 57.25 Isopropanol (99%) 35.00 Polyoxypropylene glycol-ethylene oxide addition polymer 0.05 3,5-dimethyl-l-hexyn-3-ol 0.45 Water 64.50

This invention also includes the method of forming cleaning or surface active compositions by adding 3,5- dimethyl-l-hexyn-S-ol 'to water and advantageously in admixture with a volatile alcohol in the absence of a nonvolatile detergent. Such compositions possess good cleaning ability with little rubbing and are completely volatile leaving no dirt or soil collecting residual film whatever. A 0.5 to 1 percent by volume of a water solution of 3,5-dimethyl-1-hexyn-3-ol has been found to be quite effective as a spray type glass or window cleaner.

. 0.50 percent by Weight 79 3,5-dimethyl-1-hexyn-3-ol is an effective wetting agent and is also highly volatile. This unique combination of properties in the dimethyl hexynol permits it to be used in systems such as cleaning various surfaces and thus avoids problems such as water sensitivity or rewetting as a result of the presence of a residual surface active agent since it can be readily eliminated from the system by evaporation.

3,5-dimethyl-l-hexyn-3-ol is a clear, colorless liquid having a boiling point of 150-51" C., a flash point, T.O.C., of 135 F., and is soluble in water at 20 C. to 1.1 percent by weight. 3,5-dimethyl-l-hexyn-3-ol is also miscible with. acetone, benzene, carbon tetrachloride, Cellosolve, cyclohexanone, diethylene glycol, ethanol, ethyl acetate, kerosene, methyl ethyl ketone, mineral oil, mineral spirits, monoethanolann'ne, neatsfoot oil, petroleum ether, soybean oil, and many others. 3,5-dimethyl- 1-hexyn-3-ol has a surface tension at 1 percent by weight concentration of 32.4 dynes per centimeter at 25 C., at 0.10 percent by weight concentration of 50.2 dynes per centimeter at' 25 C., and at 0.01 percent by weight concentration of 61.4 dynes per centimeter at 25 C.

The wetting time of 3,5-dimethyl-l-hexynG-ol as determined by the Braves test using a 5 g. unscoured cotton skein and a 3 g. hook at various concentrations is as follows:

0.10 percent by weight 300 0.75 percent by weight 4 1.00 percent by weight Instantaneous 3,S-dimethyl-l-hexyn-ES-ol is an elfective dispersant in polyvinyl acetate paints and can also be used in this respect to lower the amount of nonvolatile surface active agent in a similar manner as it is used to lower the amount of nonvolatile agent in cleaning compositions as described above. An example of an efiective dispersant for polyvinyl acetate paints is 0.3 percent by weight 3,5-dimethyl- 1-hexyn-3-ol, 0.2 percent by weight of a nonvolatile detergent, and 3.0 percent by weight lecithin. The 3,5-dimethyl-l-hexyn-S-ol can also be used in dry cleaning detergents and metal cleaning compounds where a volatile wetting agent is desired'or where it is desired to produce a synergistic action and reduce the amount of a nonvolatile detergentor wetting agent.

3,5-dimethyl-1-hexyn-3-ol is also useful for breaking emulsions. An emulsion was prepared from 10 ml. of kerosene and ml. of water using 0.1 percent of an alkyl phenyl ether of polyethylene glycol (Tergitol NP-35). 1 percent by volme of 3,5-dimethyl-1-hexyn-3-ol was then added and observations made after 1 hour with the followingresults:

Ml. Water Ml. Emul- Ml. Kero- Layer slon Layer sene Layer Original 88 12 0 1% 3, 5dlmethyl-1-hexyn-3-ol 89 0 11 We claim: 7

1. A cleaning composition consisting essentially of: about 0.1 percent to about 2.0 percent by volume of 3,5- dimethyl-l-hexyn-El-ol, about 0.02 percent to about 0.05 percent by volume of a non-soap synthetic organic surface active agent, said non-soap synthetic organic surface active agent being a nonvolatile detergent, and water comprising the balance of said composition.

2. A cleaning composition according to claim 1 containing in addition, about 35 percent by volume of isopropanol.

3. A cleaning composition according to claim 1 wherein said 3,5-dimethyl-1-hexyn-3-ol is about 0.48 percent by volume of said composition, andwhere said organic surface active agent is about 0.02 percent by volume of an alkyl phenyl ether of polyethylene glycol, and where said composition contains in addition about 35 percent by volume of isopropanol and about 7.25 percent by volume of diethylene glycol monoethyl ether.

4. A cleaning composition according to claim 1 where said 3,5-dimethyl-1-hexyn-3-ol is about 0.45 percent by volume of said composition, and Where said organic surface active agent is about 0.05 percent by volume of a polyoxypropylene glycol-ethylene oxide addition polymer, and where said composition contains in addition about 35 percent by volume of isopropanol.

5. A cleaning composition consisting essentially of: about 0.48 percent by Weight of 3,5 -dimethyl-1-hexyn-3-ol, about 0.02 percent by Weight of a non-soap synthetic organic surface active agent selected from the group consisting of, a nonvolatile detergent alkyl phenyl ether of polyethylene glycol, a nonvolatile detergent alkyl aryl sodium sulfonate, and a nonvolatile detergent sodium salt of condensed aryl sulfonic acid; and water comprising the balance of said composition.

References Eited in the file of this patent UNITED STATES PATENTS 1,723,169 Heydt Aug. 6, 1929 2,250,445 Bruson et al July 29, 1941 2,913,408 Pumpelly et a1 Nov. 17, 1959 FOREIGN PATENTS 706,407 Great Britain Mar. 31, 1954 OTHER REFERENCES The Stabilization of Chlorinated Organics Using Tertiary Acetylenic Alcohols and Glycols, pub. of Air Reduction Chem. Co., N.Y., p. 1, NPD-A-030505. 

1. A CLEANING COMPOSITION CONSISTING ESSENTIALLY OF: ABOUT 0.1 PERCENT TO ABOUT 2.0 PERCENT BY VOLUME OF 3,5DIMETHYL-1-HEXYN-3-OL, ABOUT 0.02 PERCENT TO ABOUT 0.05 PERCENT BY VOLUME OF A NON-SOAP SYNTHETIC ORGANIC SURFACE ACTIVE AGENT, SAID NON-SOAP SYNTHETIC ORGANIC SURFACE ACTIVE AGENT BEING A NONVOLATILE DETERGENT, AND WATER COMPRISING THE BALANCE OF SAID COMPOSITION.
 5. A CLEANING COMPOSTION CONSISTING ESSENTIALLY OF: ABOUT 0.48 PERCENT BY WEIGHT OF 3,5-DIMETHYL-1-HEXYN-3-OL, ABOUT 0.02 PERCENT BY WEIGHT OF A NON-SOAP SYNTHETIC ORGANIC SURFACE ACTIVE AGENT SELECTED FROM THE GROUP CONSISTING OF, A NONVOLATILE DETERGENT ALKYL PHENYL EHTER OF POLYETHYLENE GLYCOL, A NONVALATILE DETERGENT ALKYL ARYL SODIUM SULFONATE, AND A NONVOLATILE DETERGENT SODIUM SALT OF CONDENSED ARYL SULFONIC ACID; AND WATER COMPRISING THE BALANCE OF SAID COMPOSITION. 